{"title":"Water Spillover to Expedite Two-Electron Oxygen Reduction","authors":"Qianyi Li, Zhihao Nie, Wenqiang Wu, Hongxin Guan, Baokai Xia, Qi Huang, Jingjing Duan, Sheng Chen","doi":"10.1002/adma.202412039","DOIUrl":null,"url":null,"abstract":"<p>Limited by the activity-selectivity trade-off relationship, the electrochemical activation of small molecules (like O<sub>2</sub>, N<sub>2,</sub> and CO<sub>2</sub>) rapidly diminishes Faradaic efficiencies with elevated current densities (particularly at ampere levels). Nevertheless, some catalysts can circumvent this restriction in a two-electron oxygen reduction reaction (2e<sup>−</sup> ORR), a sustainable pathway for activating O<sub>2</sub> to hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>). Here we report 2e<sup>−</sup> ORR expedited in a fluorine-bridged copper metal–organic framework catalyst, arising from the water spillover effect. Through <i>operando</i> spectroscopies, kinetic and theoretical characterizations, it demonstrates that under neutral conditions, water spillover plays a dual role in accelerating water dissociation and stabilizing the key <sup>*</sup>OOH intermediate. Benefiting from water spillover, the catalyst can expedite 2e<sup>−</sup> ORR in the current density range of 0.1–2.0 A cm<sup>−2</sup> with both high Faradaic efficiencies (99–84.9%) and H<sub>2</sub>O<sub>2</sub> yield rates (63.17–1082.26 mg h<sup>−1</sup> cm<sup>−2</sup>). Further, the feasibility of the present system has been demonstrated by scaling up to a unit module cell of 25 cm<sup>2</sup>, in combination with techno-economics simulations showing H<sub>2</sub>O<sub>2</sub> production cost strongly dependent on current densities, giving the lowest H<sub>2</sub>O<sub>2</sub> price of $0.50 kg<sup>−1</sup> at 2.0 A cm<sup>−2</sup>. This work is expected to provide an additional dimension to leverage systems independent oftraditional rules.</p>","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"37 8","pages":""},"PeriodicalIF":26.8000,"publicationDate":"2025-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Materials","FirstCategoryId":"88","ListUrlMain":"https://advanced.onlinelibrary.wiley.com/doi/10.1002/adma.202412039","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Limited by the activity-selectivity trade-off relationship, the electrochemical activation of small molecules (like O2, N2, and CO2) rapidly diminishes Faradaic efficiencies with elevated current densities (particularly at ampere levels). Nevertheless, some catalysts can circumvent this restriction in a two-electron oxygen reduction reaction (2e− ORR), a sustainable pathway for activating O2 to hydrogen peroxide (H2O2). Here we report 2e− ORR expedited in a fluorine-bridged copper metal–organic framework catalyst, arising from the water spillover effect. Through operando spectroscopies, kinetic and theoretical characterizations, it demonstrates that under neutral conditions, water spillover plays a dual role in accelerating water dissociation and stabilizing the key *OOH intermediate. Benefiting from water spillover, the catalyst can expedite 2e− ORR in the current density range of 0.1–2.0 A cm−2 with both high Faradaic efficiencies (99–84.9%) and H2O2 yield rates (63.17–1082.26 mg h−1 cm−2). Further, the feasibility of the present system has been demonstrated by scaling up to a unit module cell of 25 cm2, in combination with techno-economics simulations showing H2O2 production cost strongly dependent on current densities, giving the lowest H2O2 price of $0.50 kg−1 at 2.0 A cm−2. This work is expected to provide an additional dimension to leverage systems independent oftraditional rules.
期刊介绍:
Advanced Materials, one of the world's most prestigious journals and the foundation of the Advanced portfolio, is the home of choice for best-in-class materials science for more than 30 years. Following this fast-growing and interdisciplinary field, we are considering and publishing the most important discoveries on any and all materials from materials scientists, chemists, physicists, engineers as well as health and life scientists and bringing you the latest results and trends in modern materials-related research every week.